N-alkyl, n-allyl thiolcarbamate compositions



United States Patent 6 Claims. 01. 260-455 This invention relates to certain novel compositions of matter and ithe .use ;of zsuch compositions ,as :herbicides. More particularly, it has been found that certain alkyl N-alkenyl, N-alkyl thiolcarbamates have =valuable herbi- .;cidaltpropeities and are particularly useful as ,preeemergence ;herbicides.

{Thus the compounds of the present invention :have the ifollowingiormula:

wherein R and R are lower alkyl radicals and R is a lower alkenyl radical. Thus, the following non' lim'iting' examples illustrate various radicals which can "be em- The following non-limiting examples illustrate methods by which the compounds of the invention can be made.

(Code numbers have been assigned to the variousmornpounds and are used hereinafter):

Example I(R21 76) 4.1 g. (0.103 mole) of sodium hydroxide was dissolved in 50 cc. of water and to this solution was added 9.0 g. (0.106 mole) of N-allylethylamine and 50 cc. of ethyl ether. The mixture was cooled in an ice bath to 5 C. and then 12.8 g. (0.103 mole) of ethyl chlorothiolformate was added slowly, keeping the temperature of the reaction mixture at 5-10 C. After completion of the addition, the ether solution was separated from the water phase and was washed with 1-50 cc. portion of dilute hydrochloric acid (3 cc. of concentrated hydrochloric acid diluted to 50 cc. with water) and 1-25 cc. portion of water. It was then dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated on the steam bath with the aid of a current of air. There was obtained as a residue 16 g. (89.8% yield) of ethyl N-ethyl-N-allylthiolcarbarnate, n 1.4900.

Example II-(R2177) When the general procedure of Example I was repeated except that 9.0 g. (0.106 mole) of N-allylethylamine, 14.3 g. (0.103 mole) of n-propyl chlorothiolformate and 4.1 g. (0.103 mole) of sodium hydroxide were employed, there was obtained 16.2 g. (84.4% yield) of n-propyl-N- ethyl-N-allylthiolcarbamate, 11 1.4872.

"ice

12 Example IlI,(R-2178:)

Whenthe general procedure of Example I was repeated except that 9.0g. (0.106mole) of 'N-allylethylamine, 15.7

5 g. f(0.l03mo'le of n-butyl chlorothiolformate and "4.1 g.

(0.103 mole) of sodium hydroxide were employedythere was obtained 17.9 g. (86.4% yield) of n'-butyl N-ethyl N- allylthiolcarbamate, 'n 1.4861.

'Whenthe general procedure of Example I=was repeated except-that 40.8 g. (0.412 mole( of'N-allyl n-propylamine, 49.8 g. (0.400 mole) of ethyl chlorothiolforrnate and 16.0 g. (0.400 mole) of sodium hydroxide were employed,

there was obtained 74 g.=of ethyl "N-allyl-N n propylthiol- -car'bamate. This material was purified by fractional-distillation through an 18 -Podbielniak 'Heli Grid Column -and-61;3 g. (82% yield) of pure product, BLP. ('30-mm..)

137-138" -C., n5 1.4873, d =0.'981.

7 Example V-(R-2182) When the generalprocedure:of' ExampletI wasirepeated except :that :10g. (0.101 mole) of N-allyl-n-propylamine, ,13. 6-g. (0;098 mole) of n-propyl chlorothiolformatezand 3.9 g. (0.098m0le) of sodium hydroxide wereemployed,

there was obtained 17.3 g. (87.8% yield)- of--n;propy1.-N-

allyl-N-n-propylthiolcarbamate, -n 1.4847.

Example VI(R 2183) When'the general procedure of Example I was repeated except-that 10 g. (0.101 mole) of Nfallyl-mpropylamine,

al5 g. (0.098 mole.) of n-butyl chlorothiolforrnate and 3.9 g. (0.098 mole) of sodium hydroxide were employed, there was obtained 20.9 g. (99.1% yield) of n-butyl -N- allyl-N-n-propylthiolca-rbamate, 11 1.4825.

Exampe VII(R'-218 7) When the general procedure of Example Iwasrepeated except that 11.6 g. (0.103 mole) of N allyl-n-butylamine, 312.5 g. (0.100 mole) of ethyl chlorothiolformate and 4.0 g. (0.100 .mole) of sodium hydroxide were employed, there was obtained 17.8 g. (88.51% yield) .ofethyl N- allyl-N-n-butylthiolcarbamate, 11 5 1.4852.

Example VHI(R2188) When the general procedure of Example I was repeated except that 11.6 g. (0.103 mole) of N-allyl-n-butyllainine, 13.9 g. (0.100 mole) of n-propylchlorothiolformate.zand 4.0 g. (0.100 mole) of sodium hydroxide were employed, there was obtained 19.8 g. (92.1% yield) of n-propyl N- allyl-N-n-butylthiolcarbamate, n 1.4832.

Example IX(R2189) When the general procedure of Example I was repeated except that 11.6 g. (0.103 mole) of N-allyl-n-butylamine, 15.3 g. (0.100 mole) of n-butyl chlorothiolformate and 4.0 g. (0.100) mole) of sodium hydroxide were emplayed, there was obtained 22.0 g. (96.0% yield) of nbutyl N-allyl-N-n-butylthiolcarbamate, 11 1.4820.

The compounds of the present invention have been extensively tested as herbicides and have been particularly evaluated as pre-emergence herbicides. Pre-emergence herbicides are ordinarily used by placing a narrow band of the herbicide over the center of a seeded crop row at time of planting or before crop emerges. If the herbicide is harmless to the desired crop, seeds or seedlings, but phytotoxic to the weed seeds or seedlings most frequently encountered, the crop grows in an almost weed-free environment. Of course, the pre-ernergence herbicide may be used over the entire field, but it is normally used in a narrow band which straddles the crop row and the balance of the weeds are controlled by various cultivation methods. Generally speaking, the herbicides of the present V invention are selective toward annual grasses and broadleafed plants, and so are effective against the most common weeds but have little efiect on such valuable row crops as corn, peas and beans, although various specific compounds are selective in different ways as the following data show. The phytocidal composition may be applied to the soil in any convenient form. For instance, it can be dissolved in a solvent, such as acetone, or emulsified and sprayed onto the soil, or it can be combined with a dry inert carrier and applied as a dust or as granules; although the composition may be applied to an entire crop plot, it is generally preferred to apply it in a narrow band, say 6", over the seeded row of a newly planted crop. Generally, rates of application of from one-half to forty pounds per acre of actual area treated will be found suitable.

In one series of tests the seeds of various plants were planted in 3" diameter paper cans in Santa Cruz loam.

The cans were watered and an amount of each compound was applied as an acetone solution to each can which would correspond to a rate of application of or We claim:

1. A new compound of the formula O Rg wherein R and R are lower alkyl radicals, and R is allyl.

2. As a new compound n-propyl N-ethyl-N-allylthiolcarbamate' 3. As a new compound n-butyl N-ethyl-N-allylthiolcarbamate.

4. As a new compound ethyl N-allyl-N-n-propylthiolcarbamate.

5. As a new compound n-propyl N-allyl-N-n-propylthiolcarbamate.

6. As a new compound n-butyl N-allyl-N-n-propylthiolcarbamate.

References Cited in the file of this patent UNITED STATES PATENTS 40 pounds per acre of the actual compound under test. 2,060,733 Hunt et 1 1 1935 Similar controls were planted and all of the cans were 2,160,880 Loane et 1 Ju 6, 939 maintained in a greenhouse, watered as needed, and 2 5 2 011 Baumgarmer 1 1 124, 1951 the germination and growth of the treated cans were 2 03 575 Mathes A 26 1952 compared with the controls. Germination was reported 2,631,935 Baumgartner Mar. 17, 1953 on a scale of 0100 and growth on a scale of 0-10; 100 2,642,451 Weijlard June 16, 1953 and 10 represent, respectively, no deviation from the 2,687,348 Kosmin Aug.24, 1954 control. The following data were obtained: 2,786,866 Hook et al Mar. 26, 1957 Rate/ Peas Corn Radish Rye Grass Cucumbers Compound Acre,

pounds Ge. Gr. Ge. Gr. Ge. Gr. Ge. Gr. Ge. Gr.

40 25 2 100 10 100 10 0 0 12-2178 10 50 a 100 10 100 10 o 1o 1 40 3 9 100 10 o 0 H-2182 10 50 a 100 10 100 10 0 0 40 15 1 100 9 100 10 0 0 13-2183 10 100 4 100 10 100 10 0 10 2 Ge.=percent germination. Gr. growth 

1. A NEW COMPOUND OF THE FORMULA 